Alkylaminosiloxanes as corrosion inhibitors

ABSTRACT

The instant invention discloses a composition comprising a carrier, preferably a packaging material, and at least one compound of the formula (I) in which the general symbols are as defined in claim 1 as corrosion inhibor for protecting metallic surfaces.

The present invention relates to compositions comprising a carrier,preferably a packaging material, and alkylaminosiloxanes as corrosioninhibitors, to the use thereof in compositions for protecting metallicsurfaces and to novel alkylaminosiloxanes.

Corrodible materials, for example iron or steel, are subjected to avariety of corrosive environments between the time when they aremanufactured and the time when they actually are used in the manufactureof an intended product. Newly manufactured metallic articles frequentlyhave fresh metal surfaces which are highly susceptible to corrosion.Corrosive environments for the metals during for example shipment,storage or handling are for example air, air containing high humidity,corrosive gasses and rain or surface condensation.

Plastic packaging processes are widely used in the packaging ofarticles. While conventional packaging applications provide protectionof the article for mechanical purposes prior to sale to the ultimateconsumer, these types of packaging may require additional protection toinhibit potential damage from humid and/or corrosive environments. Forexample, the permeability of plastic packaging permits the introductionof water vapors and other potentially harmful gaseous components intothe package envelope. These corrosive components may be introduced intothe envelope during extended shipping and storage times typicallyencountered between the completion of the packaging operation and thefinal transfer of the product to the ultimate consumer. Humidenvironments are almost universally encountered with varying degrees ofseverity. Fluctuations in temperature can cause condensation of thetrapped water vapor and ultimate deposition of the condensate onmetallic surfaces, which generates corrosion. Consequently, it isusually necessary to remove the undesirable corrosion, which is presenton the surface of the material before the purchaser may satisfactorilyuse such material. This may be a very expensive and time-consumingprocess. Additionally, when the metal material is used in themanufacture of such products as painted or electroplated articles, evensmall amounts of corrosion of the metal render such metal completelyunsatisfactory for its intended purpose.

In attempts to reduce or eliminate corrosion of metal during shipmentand storage, various types of coatings and temporary protectants havebeen proposed. For example, it is possible to simply coat the metal withan oil, grease or wax. However, such types of coatings are not alwayseffective, and they may be quite undesirable due to their flammabilityor oily nature. Furthermore, such types of coatings normally must becompletely removed from the metal surface before the metal may be usedin many manufacturing processes. Such a removal naturally is timeconsuming and also requires the use of solvents, with attendant expenseand pollution problems. Although the addition of conventional corrosioninhibiting materials to such oils, greases and waxes may render suchtypes of coatings more effective, the problems associated with removalof the coating, when necessary, are not alleviated.

Solid corrosion inhibitors, present a different set of disadvantages.Particulate materials can foul certain mechanical items and can bedifficult to remove from the protected items when finally unpacked orotherwise put to use. In other applications, solid phase or liquid phasecompounds are used which are generally referred to as volatile corrosioninhibitors (VCI). Such compounds vaporize and form a relatively stablebond at the air/metal interface thus producing a very thin layer thatinhibits the electrochemical corrosion reaction. Because molecules inthe vapor phase disperse very rapidly, even at ambient conditions oreven cooler temperatures, a vapor phase corrosion inhibitor willgenerally set up an equilibrium environment rather quickly. In such anenvironment, the corrosion inhibiting compounds can reach and protectall of the items in the enclosed environment, even in the most recessedareas and cavities of the metal, much more efficiently than could solidsor liquids, which are only effective when in contact with the corrodiblesubstrate. Additionally, because of their rapid dispersal, removal ofthe protective emitted vapors from the items is unnecessary when theitems themselves are removed from their respective packages. Severaltechniques for using volatile corrosion inhibitors have evolved to date.One method comprises forming a tablet or some other solid shaped elementfrom a solid compound, which will release, the vapor phase corrosioninhibitor. In other techniques package walls or other substrates arepainted or coated with volatile corrosion inhibitor-containingcompositions, which release protective vapors. Other techniques blendvolatile corrosion inhibitor compounds with or impregnate them intomaterials such as foamed compositions so that a foamed article protectsthe items from physical shock, as well as from corrosion. Another methodcomprises the blending of volatile corrosion inhibitors with a polymerpowder which is extruded at high temperature to packaging articles whichcontain the corrosion inhibitors. Some of the liquid or solid corrosioninhibiting compounds used in such techniques include volatile moleculeslike for example triazoles; organic or inorganic nitrites, nitrates,chromates, molybdates, carbonates, carboxylates, phosphates; primary,secondary, tertiary or quaternary amines (aliphatic or aromatic) ortheir organic or inorganic acid salts. Typical vapor phase inhibitorsare for example isopropylamine, cyclohexylamine, benzylamine,allylamine, diethyl or diisopropylamine, dicyclohexylamine, piperidine,triisopropylamine, aminoalchols, dicyclohexyammonium nitrite,diisopropylammonium nitrite, dicyclohexylammonium nitrophenate,cyclohexylammonium nitrophenate, cyclohexylamine chromate,cyclohexylamine m-mononitro-benzoate, dicyclohexylamine chromate,cyclohexylamine benzoate, monoethanolamine benzoate, diethanolaminebenzoate or mixtures thereof. Examples of such references are U.S. Pat.Nos. 4,131,583; 4,275,835; 4,973,448; 5,393,457; 5,937,618 or U.S.6,033,599.

The compounds with corrosion inhibiting properties must have asufficient volatility in order to act in the vapor phase at roomtemperature. However, a high volatility is a disadvantage when thesecompounds are incorporated into organic polymeric materials at hightemperatures. Additionally, these compounds must have a high thermalstability. A lower processsing temperature is often not possible becauseof the physicochemical properties of the organic polymeric material andthe drastically reduction of the economical output.

These known volatile corrosion inhibitors do not satisfy in everyrespect the high requirements which a corrosion inhibitor is required tomeet, especially with regard to incorporation into plastics at hightemperature, generating undesired fume or bad odor.

It has now been found that a selected group of alkylaminosiloxanes isparticularly suitable for use as corrosion inhibitors for protectingmetallic surfaces.

The present invention therefore provides a composition comprising

-   -   a) a carrier, and p1 b) as corrosion inhibitor at least one        compound of the formula I    -    wherein, when n is 1,    -    R₁ is hydrogen, C₁-C₃₂alkyl, C₂-C₃₂alkenyl, C₂-C₃₂alkynyl,        unsubstituted or C₁-C₄alkyl-substituted phenyl;        C₇-C₉phenylalkyl, C₁-C₃₂alkoxy, C₂-C₃₂alkenyloxy,        C₂-C₃₂alkynyloxy, unsubstituted or C₁-C₄alkyl-substituted        C₅-C₈cycloalkyl; unsubstituted or C₁-C₄-alkyl-substituted        C₅-C₈cycloalkoxy;    -    when n is 2,    -    R₁ is C₁-C₃₂alkylene, C₂-C₃₂alkylene interrupted by oxygen;        C₅-C₈cycloalkylene or -R₁₀-O-R₁₂-O-R₁₁-,    -    when n is 3,    -    R₁ is C₁-C₃₂alkanetriyl,    -    when n is 4,    -    R₁ is C₁-C₃₂alkanetetrayl,    -    R₂, R₃ and R₄ are each independently of the others C₁-C₃₂alkyl,        C₂-C₃₂alkenyl, C₂-C₃₂alkynyl, unsubstituted or        C₁-C₄alkyl-substituted phenyl; C₇-C₉phenylalkyl,        C₇-C₉phenylalkoxy, C₁-C₃₂alkoxy, C₂-C₃₂alkenyloxy,        C₂-C₃₂alkynyloxy, unsubstituted or C₁-C₄alkyl-substituted        C₅-C₈cycloalkyl; unsubstituted or C₁-C₄alkyl-substituted        C₅-C₈cycloalkoxy;    -    with the proviso that at least one of the radicals R₂, R₃ or R₄        is C₂-C₃₂alkynyloxy,    -    R₅ is C₁-C₁₈alkylene, C₂-C₁₈alkylene which is interrupted by        oxygen; C₂-C₁₈alkenylene, C₂-C₂₀alkylidene,        C₇-C₂₀phenylalkylidene, C₅-C₈cycloalkylene, unsubstituted or        C₁-C₄alkyl-substituted phenylene,    -    R₈ and R₇ are each independently of one another hydrogen or        C₁-C₁₂alkyl,    -    R₈ is unsubstituted or C₁-C₄alkyl-substituted C₂-C₁₂alkylene;    -    R₉ is C₁-C₂₅alkyl, C₂-C₂₅alkyl interrupted by oxygen;        C₇-C₉phenylalkyl, unsubstituted or C₁-C₄alkyl-substituted        C₅-C₈cycloalkyl; unsubstituted or C₁-C₄alkyl-substituted phenyl;    -    R₁₀ and R₁₁ are each independently of one another        C₁-C₁₈alkylene, C₂-C₁₈alkylene which is interrupted by oxygen;        C₂-C₁₈alkenylene, C₂-C₂₀alkylidene, C₇-C₂₀phenylalkylidene,        C₅-C₈cycloalkylene, unsubstituted or C₁-C₄alkyl-substituted        phenylene;    -    R₁₂ is C₁-C₁₈alkylene, C₂-C₁₈alkylene which is interrupted by        oxygen; C₂-C₁₈alkenylene, C₂-C₂₀alkylidene,        C₇-C₂₀phenylalkylidene, C₅-C₈Cycloalkylene, unsubstituted or        C₁-C₄alkyl-substituted phenylene; unsubstituted or        C₁-C₄alkyl-substituted naphthylene; or    -    R₁₃, R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, R₁₉, R₂₀, R₂₁, R₂₂, R₂₃ and R₂₄        are each independently of the others C₁-C₁₈alkylene,        C₂-C₁₈alkylene which is interrupted by oxygen; C₂-C₁₈alkenylene,        C₂-C₂₀alkylidene, C₇-C₂₀phenylalkylidene, C₅-C₈cycloalkylene,        unsubstituted or C₁-C₄alkyl-substituted phenylene;    -    R₂₅ and R₂₆ are each independently of one another hydrogen,        CF₃, C₁-C₁₂alkyl or phenyl, or R₂₅ and R₂₆ together with the        linking carbon atom, form a C₅-C₈cycloalkylidene ring which is        unsubstituted or substituted by 1 to 3 C₁-C₄alkyl groups;    -    R₂₇, R₂₈, R₂₉ and R₃₀ are each independently of the others        hydrogen or C₁-C₈alkyl; and    -    n is 1, 2, 3 or 4.

Alkyl having up to 32 carbon atoms is a branched or unbranched radical,for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl,isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl,1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl,1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl,2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl,decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl,tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl,icosyl or docosyl.

Alkenyl having 2 to 32 carbon atoms is a branched or unbranched radicalsuch as, for example, vinyl, propenyl, 2-butenyl, 3-butenyl, isobutenyl,n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl,iso-dodecenyl, oleyl, n-2-octadecenyl or n-4-octadecenyl. Preference isgiven to alkenyl having 2 to 18, especially 3 to 12, for example 3 to 6,especially 3 to 4 carbon atoms.

Alkynyl having 2 to 32 carbon atoms is a branched or unbranched radicalsuch as, for example, —C═CH, propynyl (propargyl), 2-butynyl, 3-butynyl,isobutynyl, n-2,4-pentadiynyl, 3-methyl-2-butynyl, n-2-octynyl,n-2-dodecynyl, iso-dodecynyl, n-2-octadecynyl or n-4-octadecynyl.Preference is given to alkynyl having 3 to 18, especially 3 to 12, forexample 3 to 6, especially 3 to 4 carbon atoms.

C₁-C₄Alkyl-substituted phenyl, which contains preferably from 1 to 3,especially 1 or 2, alkyl groups, is, for example, o-, m- orp-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl,2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl,3,5-dimethylphenyl, 2-methyl-6-ethylphenyl, 4-tert-butylphenyl,2-ethylphenyl or 2,6-diethylphenyl.

C₇-C₉Phenylalkyl is, for example, benzyl, α-methylbenzyl,α,α-dimethylbenzyl or 2-phenylethyl. Preference is given to benzyl.

Alkoxy having up to 32 carbon atoms is a branched or unbranched radical,for example methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy,pentyloxy, isopentyloxy, hexyloxy, heptyloxy, octyloxy, decyloxy,undecyloxy, dodecyloxy, hexadecyloxy or octadecyloxy.

Alkenyloxy of 2 to 32 carbon atoms is a branched or unbranched radical,for example vinyloxy, propenyloxy, 2-butenyloxy, 3-butenyloxy,isobutenyloxy, n-2,4-pentadienyloxy, 3-methyl-2-butenyloxy,n-2-octenyloxy, n-2-dodecenyloxy, isododecenyloxy, oleyloxy,n-2-octadecenyloxy or n-4-octadecenyloxy. It is preferred to usealkenyloxy of 3 to 12, in particular of 3 to 6, most preferably of 3 to4, carbon atoms.

Alkynyloxy having 2 to 32 carbon atoms is a branched or unbranchedradical such as, for example, vinyloxy, propynyloxy, 2-butynyloxy,3-butynyloxy, isobutynyloxy, n-2,4-pentadiynyloxy,3-methyl-2-butynyloxy, n-2-octynyloxy, n-2-dodecynyloxy,iso-dodecynyloy, n-2-octadecynyloxy or n-4-octadecynyloxy. Preference isgiven to alkynyloxy having 3 to 18, especially 3 to 12, for example 3 to6, especially 3 to 4 carbon atoms.

Unsubstituted or C₁-C₄alkyl-substituted C₅-C₈cycloalkyl is, for example,cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl,methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl,tert-butylcyclohexyl, cycloheptyl or cyclooctyl. Preference is given tocyclohexyl.

Unsubstituted or C₁-C₄alkyl-substituted C₅-C₈cycloalkoxy is, forexample, cyclopentoxy, methylcyclopentoxy, dimethylcyclopentoxy,cyclohexyloxy, methylcyclohexyloxy, dimethylcyclohexyloxy,trimethylcyclohexyloxy, tert-butylcyclohexyloxy, cycloheptyloxy orcyclooctyloxy. Preference is given to cyclohexyloxy.

C₁-C₃₂Alkylene is a branched or unbranched radical, for examplemethylene, ethylene, propylene, tetramethylene, pentamethylene,hexamethylene, heptamethylene, octamethylene, decamethylene,dodecamethylene or octadecamethylene.

C₂-C₃₂Alkylene which is interrupted by oxygen is, for example,—CH₂—O—CH₂—, —CH₂—O—CH₂CH₂—, —CH₂CH₂—O—CH₂CH₂—,—CH₂CH₂—O—CH₂CH₂—O—CH₂CH₂—, —CH₂CH₂—(O—CH₂CH₂—)₂O—CH₂CH₂—,—CH₂CH₂—(O—CH₂CH₂—)₃O—CH₂CH₂— or —CH₂CH₂—(O—CH₂CH₂—)₄O—CH₂CH₂—.

C₅-C₈Cycloalkylene is a saturated hydrocarbon group having two freevalences and at least one ring unit and is, for example, cyclopentylene,cyclohexylene, cycloheptylene or cyclooctylene. Preference is given tocyclohexylene.

C₁-C₃₂Alkanetriyl is for example

C₁-C₃₂Alkanetetrayl is for example

C₇-C₉Phenylalkoxy is, for example, benzyloxy, α-methylbenzyloxy,α,α-dimethylbenzyloxy or 2-phenylethoxy. Preference is given tobenzyloxy.

C₂-C₁₈Alkenylene is a branched or unbranched radical such as, forexample, vinylene, propenylene, 2-butenylene, 3-butenylene,isobutenylene, n-2,4-pentadienylene, 3-methyl-2-butenylene,n-2-octenylene, n-2-dodecenylene, iso-dodecenylene, oleylene,n-2-octadecenylene or n-4-octadecenylene. Preference is given to alkenyl3 to 12, for example 3 to 6, especially 3 to 4 carbon atoms.

Alkylidene having from 2 to 20 carbon atoms is, for example, ethylidene,propylidene, butylidene, pentylidene, 4-methylpentylidene, heptylidene,nonylidene, tridecylidene, nonadecylidene, 1-methylethylidene,1-ethylpropylidene or 1-ethylpentylidene. Preference is given toC₂-C₈alkylidene.

Phenylalkylidene having from 7 to 20 carbon atoms is, for example,benzylidene, 2-phenyl-ethylidene or 1-phenyl-2-hexylidene. Preference isgiven to C₇-C₉phenylalkylidene.

Phenylene or naphthylene each unsubstituted or substituted by C₁-C₄alkylis, for example, 1,2-, 1,3- or 1,4-phenylene; 1,2-, 1,3-, 1,4-, 1,6-,1,7-, 2,6- or 2,7-naphthylene.

Unsubstituted or C₁-C₄alkyl-substituted C₂-C₁₂alkylene is a branched orunbranched radical, for example methylene, ethylene, propylene,2-methylpropylene, tetramethylene, 2,2-di-methylbutylene,pentamethylene, hexamethylene, heptamethylene, octamethylene,decamethylene, dodecamethylene or octadecamethylene.

C₂-C₂₅Alkyl which is interrupted by oxygen is, for example, CH₃—O—CH₂—,CH₃—O—CH₂CH₂—, CH₃CH₂—O—CH₂CH₂—, CH₃CH₂—O—CH₂CH₂—O—CH₂CH₂—,CH₃CH₂—(O—CH₂CH₂—)₂O—CH₂CH₂—, CH₃CH₂—(O—CH₂CH₂—)₃O—CH₂CH₂— orCH₃CH₂—(O—CH₂CH₂—)₄O—CH₂CH₂—.

A C₅-C₈cycloalkylidene ring which is unsubstituted or substituted by 1to 3 C₁-C₄alkyl groups, which contains preferably 1 or 2 branched orunbranched alkyl groups, is, for example, cyclopentylidene,methylcyclopentylidene, dimethylcyclopentylidene, cyclohexylidene,methylcyclohexylidene, dimethylcyclohexylidene,trimethylcyclohexylidene, tert-butylcyclohexylidene, cycloheptylidene orcyclooctylidene. Preference is given to cyclohexylidene.

Preferred compositions comprise compounds of the formula I, wherein,when n is 1, R₁ is hydrogen, C₁-C₃₂alkyl, C₂-C₃₂alkenyl, C₃-C₃₂alkynyl,unsubstituted or C₁-C₄alkyl-substituted phenyl; C₇-C₉phenylalkyl,C₁-C₃₂alkoxy, C₂-C₃₂alkenyloxy, C₂-C₃₂alkynyloxy, unsubstituted orC₁-C₄alkyl-substituted C₅-C₈cycloalkyl; unsubstituted orC₁-C₄alkyl-substituted C₅-C₈cycloalkoxy;

-   -   when n is 2,    -   R₁ is C₁-C₃₂alkylene, C₂-C₁₈alkylene interrupted by oxygen;        C₅-C₈cycloalkylene or -R₁₀-O-R₁₂-O-R₁₁-.    -   when n is 3,    -   R₁ is C₁-C₃₂alkanetriyl,    -   when n is 4,    -   R₁ is C₁-C₃₂alkanetetrayl    -   R₂, R₃ and R₄ are each independently of the others C₁-C₃₂alkyl,        C₂-C₃₂alkenyl, C₃-C₃₂alkynyl, unsubstituted or        C₁-C₄alkyl-substituted phenyl; C₇-C₉phenylalkyl,        C₇-C₉phenylalkoxy, C₁-C₃₂alkoxy, C₂-C₃₂alkenyloxy,        C₂-C₃₂alkynyloxy, unsubstituted or C₁-C₄alkyl-substituted        C₅-C₈cycloalkyl; unsubstituted or C₁-C₄alkyl-substituted        C₅-C₈cycloalkoxy;    -    with the proviso that at least one of the radicals R₂, R₃ or R₄        is C₂-C₃₂alkynyloxy,    -   R₅ is C₁-C₁₈alkylene, C₂-C₁₈alkylene which is interrupted by        oxygen; C₂-C₁₈alkenylene, C₂-C₂₀alkylidene,        C₇-C₂₀phenylalkylidene, C₅-C₈cycloalkylene, unsubstituted or        C₁-C₄alkyl-substituted phenylene,    -   R₆ and R₇ are each independently of one another hydrogen or        C₁-C₁₂alkyl,    -   R₈ is unsubstituted or C₁-C₄alkyl-substituted C₂-C₁₂alkylene;    -   R₉ is C₁-C₂₅alkyl, C₂-C₂₅alkyl interrupted by oxygen;        C₇-C₉phenylalkyl, unsubstituted or C₁-C₄alkyl-substituted        C₅-C₈cycloalkyl; unsubstituted or C₁-C₄alkyl-substituted phenyl;    -   R₁₀ and R₁₁ are each independently of one another        C₁-C₁₈alkylene, C₂-C₁₈alkylene which is interrupted by oxygen;        C₂-C₁₈alkenylene, C₂-C₂₀alkylidene, C₇-C₂₀phenylalkylidene,        C₅-C₈cycloalkylene, unsubstituted or C₁-C₄alkyl-substituted        phenylene;    -   R₁₂ is C₁-C₁₈alkylene, C₂-C₁₆alkylene which is interrupted by        oxygen; C₂-C₁₈alkenylene, C₂-C₂₀alkylidene,        C₇-C₂₀phenylalkylidene, C₅-C₈cycloalkylene, unsubstituted or        C₁-C₄alkyl-substituted phenylene; unsubstituted or        C₁-C₄alkyl-substituted naphthylene; or    -   R₁₃, R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, R₁₉, R₂₀, R₂₁, R₂₂, R₂₃ and R₂₄        are each independently of the others C₁-C₁₈alkylene,        C₂-C₁₈alkylene which is interrupted by oxygen; C₂-C₁₈alkenylene,        C₂-C₂₀alkylidene, C₇-C₂₀phenylalkylidene, C₅-C₈cycloalkylene,        unsubstituted or C₁-C₄alkyl-substituted phenylene;    -   R₂₅ and R₂₆ are each independently of one another hydrogen, CF₃,        C₁-C₁₂alkyl or phenyl, or    -   R₂₅ and R₂₆ together with the linking carbon atom, form a        C₅-C₈cycloalkylidene ring which is unsubstituted or substituted        by 1 to 3 C₁-C₄alkyl groups;    -   R₂₇ is hydrogen or C₁-C₈alkyl; and    -   n is 1, 2, 3 or 4.

Interesting compositions are those comprising compounds of formula Iwherein, when n is 1, R₁ is hydrogen, C₁-C₁₈alkyl, C₂-C₁₈alkenyl,C₃-C₁₈alkynyl, unsubstituted or C₁-C₄alkyl-substituted phenyl;C₇-C₉phenylalkyl, C₁-C₁₀alkoxy, C₂-C₁₈alkenyloxy, C₂-C₁₈alkynyloxy,unsubstituted or C₁-C₄alkyl-substituted C₅-C₈cycloalkyl; unsubstitutedor C₁-C₄alkyl-substituted C₅-C₈cycloalkoxy;

-   -    when n is 2,    -   R₁ is C₁-C₁₈alkylene, C₄-C₁₈alkylene interrupted by oxygen;        C₅-C₇cycloalkylene or -R₁₀-O-R₁₂-O-R₁₁-,    -    when n is 3,    -   R₁ is C₁-C₁₈alkanetriyl or    -    when n is 4,    -   R₁ is C₁-C₁₈alkanetetrayl,    -   R₂, R₃ and R₄ are each independently of the others C₁-C₁₈alkyl,        C₂-C₁₈alkenyl, C₃-C₁₈alkynyl, unsubstituted or        C₁-C₄alkyl-substituted phenyl; C₇-C₉phenylalkyl,        C₇-C₉phenylalkoxy, C₁-C₁₈alkoxy, C₂-C₁₈alkenyloxy,        C₂-C₁₈alkynyloxy, unsubstituted or C₁-C₄alkyl-substituted        C₅-C₈cycloalkyl; unsubstituted or C₁-C₄alkyl-substituted        C₅-C₈cycloalkoxy;    -    with the proviso that at least one of the radicals R₂, R₃ or R₄        is C₂-C₁₈alkynyloxy,    -   R₅ is C₁-C₁₂alkylene, C₄-C₁₂alkylene which is interrupted by        oxygen; C₂-C₁₂alkenylene, C₂-C₁₂alkylidene,        C₇-C₁₂phenylalkylidene, C₅-C₈cycloalkylene, unsubstituted or        C₁-C₄alkyl-substituted phenylene,    -   R₆ and R₇ are each independently of one another hydrogen or        C₁-C₈alkyl,    -   R₈ is unsubstituted or C₁-C₄alkyl-substituted C₂-C₈alkylene;    -   R₉ is C₁-C₁₈alkyl, C₄-C₁₈alkyl interrupted by oxygen;        C₇-C₉phenylalkyl, unsubstituted or C₁-C₄alkyl-substituted        C₅-C₈cycloalkyl; unsubstituted or C₁-C₄alkyl-substituted phenyl;    -   R₁₀ and R₁₁ are each independently of one another        C₁-C₁₂alkylene, C₄-C₁₈alkylene which is interrupted by oxygen;        C₂-C₁₈alkenylene, C₂-C₁₂alkylidene, C₇-C₁₂phenylalkylidene,        C₅-C₈cycloalkylene, unsubstituted or C₁-C₄alkyl-substituted        phenylene;    -   R₁₂ is C₁-C₁₈alkylene, C₄-C₁₈alkylene which is interrupted by        oxygen; C₂-C₁₈alkenylene, C₂-C₁₂alkylidene,        C₇-C₁₂phenylalkylidene, C₅-C₈cycloalkylene, unsubstituted or        C₁-C₄alkyl-substituted phenylene; unsubstituted or        C₁-C₄alkyl-substituted naphthylene; or    -   R₁₃, R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, R₁₉ , R₂₀, R₂₁, R₂₂, R₂₃ and R₂₄        are each independently of the others C₁-C₁₈alkylene,        C₄-C₁₈alkylene which is interrupted by oxygen; C₂-C₁₈alkenylene,        C₂-C₁₂alkylidene, C₇-C₁₂phenylalkylidene, C₅-C₈cycloalkylene,        unsubstituted or C₁-C₄alkyl-substituted phenylene;    -   R₂₅ and R₂₆ are each independently of one another hydrogen, CF₃,        C₁-C₁₂alkyl or phenyl, or    -   R₂₅ and R₂₆ together with the linking carbon atom, form a        C₅-C₈cycloalkylidene ring which is unsubstituted or substituted        by 1 to 3 C₁-C₄alkyl groups; and    -   n is 1, 2, 3 or 4.

Likewise of interest is a composition comprising compounds of formula Iwherein n is 1 or 2.

Of special interest is a composition comprising compounds of formula Iwherein at least one of the radicals R₂, R₃ or R₄ is C₃-C₄alkynyloxy,

-   -   R₅ is C₁-C₁₂alkylene, C₄-C₁₂alkylene which is interrupted by        oxygen; or C₂-C₁₂alkenylene,    -   R₆ and R₇ are each independently of one another C₁-C₄alkyl, and    -   R₈ is C₄-C₆alkylene.

Likewise of special interest is a composition comprising compounds offormula I wherein, when n is 1,

-   -   R₁ is C₁-C₁₈alkyl, C₂-C₈alkenyl, C₃-C₈alkynyl, phenyl; benzyl,        C₁-C₁₂alkoxy, C₂-C₁₂alkenyloxy, C₂-C₁₂alkynyloxy,        C₅-C₈cycloalkyl, C₅-C₈cycloalkoxy,    -    when n is 2,    -   R₁ is C₂-C₁₈alkylene, C₄-C₁₈alkylene interrupted by oxygen; or        -R₁₀-O-R₁₂-O-R₁₁-,    -   when n is 3,    -   R₁ is C₄-C₁₂alkanetriyl or    -   when n is 4,    -   R₁ is C₅-C₁₂alkanetetrayl,    -   R₂, R₃ and R₄ are each independently of the others C₁-C₈alkyl,        C₂-C₈alkenyl, C₃-C₈alkynyl, phenyl; benzyl, phenylethoxy,        C₁-C₁₂alkoxy, C₃-C₁₂alkenyloxy, C₃-C₁₂alkynyloxy,        C₅-C₈cycloalkyl, C₅-C₈cycloalkoxy,    -    with the proviso that at least one of the radicals R₂, R₃ or R₄        is C₃-C₁₂alkynyloxy,    -   R₅ is C₂-C₈alkylene, C₄-C₈alkylene which is interrupted by        oxygen; C₄-C₈alkenylene, C₂-C₈alkylidene, benzylidene,        cyclohexylene or phenylene,    -   R₆ and R₇ are each independently of one another C₁-C₄alkyl,    -   R₈ is C₄-C₆alkylene,    -   R₁₀ and R₁₁ are each independently of one another C₂-C₈alkylene,        C₄-C₁₈alkylene which is interrupted by oxygen; C₂-C₂alkenylene,        C₂-C₈alkylidene, benzylidene, cyclohexylene or phenylene,    -   R₁₂ is C₂-C₁₂alkylene, C₄-C₁₂alkylene which is interrupted by        oxygen; C₂-C₁₂alkenylene, C₂-C₈alkylidene, benzylidene,        cyclohexylene, unsubstituted, phenylene, naphthylene or    -   R₁₃, R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, R₁₉, R₂₀, R₂₁, R₂₂, R₂₃ and R₂₄        are each independently of the others C₂-C₈alkylene,        C₄-C₈alkylene which is interrupted by oxygen; C₄-C₆alkenylene,        C₂-C₈alkylidene, benzylidene, cyclohexylene or phenylene,    -   R₂₅ and R₂₆ are each independently of one another hydrogen or        C₁-C₄alkyl, or R₂₅ and R₂₆ together with the linking carbon        atom, form a cyclohexylidene ring; and    -   n is 1, 2, 3 or 4.

Special preference is given to a composition comprising compounds offormula I wherein, when n is 1,

-   -   R₁ is C₁-C₁₈alkyl, phenyl; benzyl, C₁-C₁₂alkoxy,        C₃-C₆alkynyloxy,    -   when n is 2,    -   R₁ is C₄-C₁₂alkylene, C₄-C₁₂alkylene interrupted by oxygen; or        -R₁₀-O-R₁₂-O-R₁₁-.    -   when n is 3,    -   R₁ is C₄-C₈alkanetriyl,    -   when n is 4,    -   R₁ is C₅-C₈alkanetetrayl,    -   R₂, R₃ and R₄ are each independently of the others C₁-C₆alkyl,        phenyl; benzyl, phenylethoxy, C₁-C₄alkoxy, C₃-C₈alkenyloxy,        C₃-C₈alkynyloxy, cyclohexyl, cyclohexyloxy,    -    with the proviso that at least one of the radicals R₂, R₃ or R₄        is C₃-C₈alkynyloxy,    -   R₅ is C₂-C₈alkylene or C₄-C₈alkylene which is interrupted by        oxygen;    -   R₆ and R₇ are each independently of one another C₁-C₄alkyl,    -   R₈ is C₄-C₅alkylene,    -   R₁₀ and R₁₁ are each independently of one another C₂-C₈alkylene        or C₄-C₁₈alkylene which is interrupted by oxygen;    -   R₁₂ is C₂-C₈alkylene, C₄-C₈alkylene which is interrupted by        oxygen; or    -   R₂₅ and R₂₆ are each independently of one another hydrogen or        C₁-C₄alkyl, or R₂₅ and R₂₆ together with the linking carbon        atom, form a cyclohexylidene ring; and    -   n is 1, 2, 3 or 4.

Compositions of very particular interest are those in which component(b) is a compound of the formula I wherein, when n is 1,

-   -   R₁ C₁-C₁₂alkyl, phenyl or    -   when n is 2,    -   R₁ is C₆-C₁₀alkylene or -R₁₀-O-R₁₂-O-R₁₁-,    -   R₂, R₃ and R₄ are each independently of the others C₁-C₃alkyl,        phenyl; phenylethoxy, C₃-C₄alkynyloxy;    -    with the proviso that at least one of the radicals R₂, R₃ or R₄        is C₃-C₄alkynyloxy,    -   R₅ is C₂-C₄alkylene,    -   R₆ and R₇ are each independently of one another methyl or ethyl,    -   R₈ is C₄-C₅alkylene,    -   R₁₀ and R₁₁ are each independently of one another C₂-C₄alkylene,    -   R₁₂ is    -   R₂₅ and R₂₆ are each independently of one another hydrogen or        C₁-C₄alkyl; and    -   n is 1 or 2.

Most of the compounds of the formula I are known or can be prepared inanalogy to the process disclosed for example in U.S. Pat. No. 4,406,807.

The compounds of the formula I are suitable as corrosion inhibitors incarriers for protecting metallic surfaces, for example iron, steel,copper, zinc or aluminum, and their alloys.

A preferred carrier is for example a packaging material, an oil, agrease, a wax, a gel, an emulsion, a surface-coating material comprisingan organic film-forming binder, an inorganic solid, a paper, a fabric, anatural, semi-synthetic or synthetic polymer.

Preferred organic film-forming binders are epoxy resins, polyurethaneresins, polyester resins, acrylic resins and copolymer resins thereof,polyvinyl resins alkyd resins or mixtures of such resins.

Examples for inorganic solids are clays, silica or zeolithes.

Examples of natural, semi-synthetic or synthetic polymers are:

-   1. Polymers of monoolefins and diolefins, for example polypropylene,    polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene,    polyvinylcyclohexane, polyisoprene or polybutadiene, as well as    polymers of cycloolefins, for instance of cyclopentene or    norbornene, polyethylene (which optionally can be crosslinked), for    example high density polyethylene (HDPE), high density and high    molecular weight polyethylene (HDPE-HMW), high density and ultrahigh    molecular weight polyethylene (HDPE-UHMW), medium density    polyethylene (MDPE), low density polyethylene (LDPE), linear low    density polyethylene (LLDPE), (VLDPE) and (ULDPE).-    Polyolefins, i.e. the polymers of monoolefins exemplified in the    preceding paragraph, preferably polyethylene and polypropylene, can    be prepared by different, and especially by the following, methods:    -   a) radical polymerisation (normally under high pressure and at        elevated temperature).    -   b) catalytic polymerisation using a catalyst that normally        contains one or more than one metal of groups IVb, Vb, VIb or        VIII of the Periodic Table. These metals usually have one or        more than one ligand, typically oxides, halides, alcoholates,        esters, ethers, amines, alkyls, alkenyls and/or aryls that may        be either π- or σ-coordinated. These metal complexes may be in        the free form or fixed on substrates, typically on activated        magnesium chloride, titanium(III) chloride, alumina or silicon        oxide. These catalysts may be soluble or insoluble in the        polymerisation medium. The catalysts can be used by themselves        in the polymerisation or further activators may be used,        typically metal alkyls, metal hydrides, metal alkyl halides,        metal alkyl oxides or metal alkyloxanes, said metals being        elements of groups Ia, IIa and/or IIIa of the Periodic Table.        The activators may be modified conveniently with further ester,        ether, amine or silyl ether groups. These catalyst systems are        usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta),        TNZ (DuPont), metallocene or single site catalysts (SSC).-   2. Mixtures of the polymers mentioned under 1), for example mixtures    of polypropylene with polyisobutylene, polypropylene with    polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of    different types of polyethylene (for example LDPE/HDPE).-   3. Copolymers of monoolefins and diolefins with each other or with    other vinyl monomers, for example ethylene/propylene copolymers,    linear low density polyethylene (LLDPE) and mixtures thereof with    low density polyethylene (LDPE), propylene/but-1-ene copolymers,    propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,    ethylene/hexene copolymers, ethylene/methylpentene copolymers,    ethylene/heptene copolymers, ethylene/octene copolymers,    ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin    copolymers (e.g. ethylene/norbornene like COC), ethylene/1-olefins    copolymers, where the 1-olefin is generated in-situ;    propylene/butadiene copolymers, isobutylene/isoprene copolymers,    ethylene/vinylcyclohexene copolymers, ethylene/alkyl acrylate    copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl    acetate copolymers or ethylene/acrylic acid copolymers and their    salts (ionomers) as well as terpolymers of ethylene with propylene    and a diene such as hexadiene, dicyclopentadiene or    ethylidene-norbornene; and mixtures of such copolymers with one    another and with polymers mentioned in 1) above, for example    polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl    acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers    (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random    polyalkylene/carbon monoxide copolymers and mixtures thereof with    other polymers, for example polyamides.-   4. Hydrocarbon resins (for example C₅-C₉) including hydrogenated    modifications thereof (e.g. tackifiers) and mixtures of    polyalkylenes and starch. Homopolymers and copolymers from 1.)-4.)    may have any stereostructure including syndiotactic, isotactic,    hemi-isotactic or atactic; where atactic polymers are preferred.    Stereoblock polymers are also included.-   5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).-   6. Aromatic homopolymers and copolymers derived from vinyl aromatic    monomers including styrene, α-methylstyrene, all isomers of vinyl    toluene, especially p-vinyltoluene, all isomers of ethyl styrene,    propyl styrene, vinyl biphenyl, vinyl naphthalene, and vinyl    anthracene, and mixtures thereof. Homopolymers and copolymers may    have any stereostructure including syndiotactic, isotactic,    hemi-isotactic or atactic; where atactic polymers are preferred.    Stereoblock polymers are also included.-   6a. Copolymers including aforementioned vinyl aromatic monomers and    comonomers selected from ethylene, propylene, dienes, nitriles,    acids, maleic anhydrides, maleimides, vinyl acetate and vinyl    chloride or acrylic derivatives and mixtures thereof, for example    styrene/butadiene, styrene/acrylonitrile, styrene/ethylene    (interpolymers), styrene/alkyl methacrylate, styrene/butadiene/alkyl    acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic    anhydride, styrene/acrylonitrile/methyl acrylate; mixtures of high    impact strength of styrene copolymers and another polymer, for    example a polyacrylate, a diene polymer or an    ethylene/propylene/diene terpolymer; and block copolymers of styrene    such as styrene/butadiene/styrene, styrene/isoprene/styrene,    styrene/ethylene/butylene/styrene or    styrene/ethylene/propylene/styrene.-   6b. Hydrogenated aromatic polymers derived from hydrogenation of    polymers mentioned under 6.), especially including    polycyclohexylethylene (PCHE) prepared by hydrogenating atactic    polystyrene, often referred to as polyvinylcyclohexane (PVCH).-   6c. Hydrogenated aromatic polymers derived from hydrogenation of    polymers mentioned under 6a.).-    Homopolymers and copolymers may have any stereostructure including    syndiotactic, isotactic, hemi-isotactic or atactic; where atactic    polymers are preferred. Stereoblock polymers are also included.-   7. Graft copolymers of vinyl aromatic monomers such as styrene or    α-methylstyrene, for example styrene on polybutadiene, styrene on    polybutadiene-styrene or polybutadiene-acrylonitrile copolymers;    styrene and acrylonitrile (or methacrylonitrile) on polybutadiene;    styrene, acrylonitrile and methyl methacrylate on polybutadiene;    styrene and maleic anhydride on polybutadiene; styrene,    acrylonitrile and maleic anhydride or maleimide on polybutadiene;    styrene and maleimide on polybutadiene; styrene and alkyl acrylates    or methacrylates on polybutadiene; styrene and acrylonitrile on    ethylene/propylene/diene terpolymers; styrene and acrylonitrile on    polyalkyl acrylates or polyalkyl methacrylates, styrene and    acrylonitrile on acrylate/butadiene copolymers, as well as mixtures    thereof with the copolymers listed under 6), for example the    copolymer mixtures known as ABS, MBS, ASA or AES polymers.-   8. Halogen-containing polymers such as polychloroprene, chlorinated    rubbers, chlorinated and brominated copolymer of    isobutylene-isoprene (halobutyl rubber), chlorinated or    sulfochlorinated polyethylene, copolymers of ethylene and    chlorinated ethylene, epichlorohydrin homo- and copolymers,    especially polymers of halogen-containing vinyl compounds, for    example polyvinyl chloride, polyvinylidene chloride, polyvinyl    fluoride, polyvinylidene fluoride, as well as copolymers thereof    such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl    acetate or vinylidene chloride/vinyl acetate copolymers.-   9. Polymers derived from α,β-unsaturated acids and derivatives    thereof such as polyacrylates and polymethacrylates; polymethyl    methacrylates, polyacrylamides and polyacrylonitriles,    impact-modified with butyl acrylate.-   10. Copolymers of the monomers mentioned under 9) with each other or    with other unsaturated monomers, for example acrylonitrile/    butadiene copolymers, acrylonitrile/alkyl acrylate copolymers,    acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide    copolymers or acrylonitrile/ alkyl methacrylate/butadiene    terpolymers.-   11. Polymers derived from unsaturated alcohols and amines or the    acyl derivatives or acetals thereof, for example polyvinyl alcohol,    polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl    maleate, polyvinyl butyral, polyallyl phthalate or polyallyl    melamine; as well as their copolymers with olefins mentioned in 1)    above.-   12. Homopolymers and copolymers of cyclic ethers such as    polyalkylene glycols, polyethylene oxide, polypropylene oxide or    copolymers thereof with bisglycidyl ethers.-   13. Polyacetals such as polyoxymethylene and those polyoxymethylenes    which contain ethylene oxide as a comonomer; polyacetals modified    with thermoplastic polyurethanes, acrylates or MBS.-   14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene    oxides with styrene polymers or polyamides.-   15. Polyurethanes derived from hydroxyl-terminated polyethers,    polyesters or polybutadienes on the one hand and aliphatic or    aromatic polyisocyanates on the other, as well as precursors    thereof.-   16. Polyamides and copolyamides derived from diamines and    dicarboxylic acids and/or from aminocarboxylic acids or the    corresponding lactams, for example polyamide 4, polyamide 6,    polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide    12, aromatic polyamides starting from m-xylene diamine and adipic    acid; polyamides prepared from hexamethylenediamine and isophthalic    or/and terephthalic acid and with or without an elastomer as    modifier, for example poly-2,4,4,-trimethylhexamethylene    terephthalamide or poly-m-phenylene iso-phthalamide; and also block    copolymers of the aforementioned polyamides with polyolefins, olefin    copolymers, ionomers or chemically bonded or grafted elastomers; or    with polyethers, e.g. with polyethylene glycol, polypropylene glycol    or polytetramethylene glycol; as well as polyamides or copolyamides    modified with EPDM or ABS; and polyamides condensed during    processing (RIM polyamide systems).-   17. Polyureas, polyimides, polyamide-imides, polyetherimids,    polyesterimids, polyhydantoins and polybenzimidazoles.-   18. Polyesters derived from dicarboxylic acids and diols and/or from    hydroxycarboxylic acids or the corresponding lactones, for example    polyethylene terephthalate, polybutylene terephthalate,    poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene    naphthalate (PAN) and polyhydroxybenzoates, as well as block    copolyether esters derived from hydroxyl-terminated polyethers; and    also polyesters modified with polycarbonates or MBS.-   19. Polycarbonates and polyester carbonates.-   20. Polyketones.-   21. Polysulfones, polyether sulfones and polyether ketones.-   22. Crosslinked polymers derived from aldehydes on the one hand and    phenols, ureas and melamines on the other hand, such as    phenol/formaldehyde resins, urea/formaldehyde resins and    melamine/formaldehyde resins.-   23. Drying and non-drying alkyd resins.-   24. Unsaturated polyester resins derived from copolyesters of    saturated and unsaturated dicarboxylic acids with polyhydric    alcohols and vinyl compounds as crosslinking agents, and also    halogen-containing modifications thereof of low flammability.-   25. Crosslinkable acrylic resins derived from substituted acrylates,    for example epoxy acrylates, urethane acrylates or polyester    acrylates.-   26. Alkyd resins, polyester resins and acrylate resins crosslinked    with melamine resins, urea resins, isocyanates, isocyanurates,    polyisocyanates or epoxy resins.-   27. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic,    heterocyclic or aromatic glycidyl compounds, e.g. products of    diglycidyl ethers of bisphenol A and bisphenol F, which are    crosslinked with customary hardeners such as anhydrides or amines,    with or without accelerators.-   28. Blends of the aforementioned polymers (polyblends), for example    PP/EPDM, Poly-amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS,    PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic    PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA    6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or    PBT/PET/PC.

Of special interest are compositions comprising as carrier a syntheticpolymer, especially a polyolefin, in particular polyethylene,polypropylene or polybutylene or a copolymer thereof with a monoolefinor diolefin.

Also of interest are compositions comprising as carrier biodegradablepolymers like for example poly-3-hydroxybutyrate, polysaccharide,polyethylene succinate, polybutylene succinate, polybutylenesuccinate/adipate, polybutylene succinate/carbonate, polybutylenesuccinate/terephthalate, polycaprolactone, polylactic acid, polyvinylalcohol, starch, starch-based PCL, starch-based polyvinyl alcohol,cellulose acetate, or chitosan-cellulose.

The compounds of the formula I are preferably added to the carrier in anamount of from 0.02 to 5%, in particular from 0.10 to 5%, for examplefrom 0.50 to 3%, based on the weight of the carrier.

In addition to components (a) and (b) the novel compositions maycomprise further additives (costabilizers) such as, for example, thefollowing:

-   1. Antioxidants-   1.1. Alkylated monophenols, for example    2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol,    2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,    2,6-di-tert-butyl-4-isobutylphenol,    2,6-dicyclopentyl-4-methylphenol,    2-(α-methylcyclohexyl)-4,6-dimethylphenol,    2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,    2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are    linear or branched in the side chains, for example    2,6-di-nonyl-4-methylphenol,    2,4-dimethyl-6-(1′-methylundec-1′-yl)phenol,    2,4-dimethyl-6-(1′-methylheptadec-1′-yl)phenol,    2,4-dimethyl-6-(1′-methyltridec-1′-yl)phenol and mixtures thereof.-   1.2. Alkylthiomethylphenols, for example    2,4-dioctylthiomethyl-6-tert-butylphenol,    2,4-dioctylthiomethyl-6-methylphenol,    2,4-dioctylthiomethyl-6-ethylphenol,    2,6-di-dodecylthiomethyl-4-nonylphenol.-   1.3. Hydroquinones and alkylated hydroquinones, for example    2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,    2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenyl,    2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,    3,5-di-tert-butyl-4-hydroxyanisole,    3,5-di-tert-butyl-4-hydroxyphenyl stearate,    bis(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.-   1.4. Tocopherols, for example α-tocopherol, β-tocopherol,    γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E).-   1.5. Hydroxylated thiodiphenyl ethers, for example    2,2′-thiobis(6-tert-butyl-4-methylphenol),    2,2′-thiobis(4-octylphenol),    4,4′-thiobis(6-tert-butyl-3-methylphenol),    4,4′-thiobis(6-tert-butyl-2-methylphenol),    4,4′-thiobis(3,6-di-sec-amylphenol),    4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide.-   1.6. Alkylidenebisphenols, for example    2,2′-methylenebis(6-tert-butyl-4-methylphenol),    2,2′-methylenebis(6-tert-butyl-4-ethylphenol),    2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol],    2,2′-methylenebis(4-methyl-6-cyclohexylphenol),    2,2′-methylenebis(6-nonyl-4-methylphenol),    2,2′-methylenebis(4,6-di-tert-butylphenol),    2,2′-ethylidenebis(4,6-di-tert-butylphenol),    2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol),    2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],    2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],    4,4′-methylenebis(2,6-di-tert-butylphenol),    4,4′-methylenebis(6-tert-butyl-2-methylphenol),    1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl) butane,    2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,    1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,    1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane,    ethylene glycol    bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate],    bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,    bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,    1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,    2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl) propane,    2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane,    1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.-   1.7. O- N- and S-benzyl compounds, for example    3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether,    octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,    tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,    tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,    bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate,    bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide,    isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.-   1.8. Hydroxybenzylated malonates, for example    dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl) malonate,    di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate,    didodecylmercaptoethyl-2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl)    malonate, bis[4-(1,1,3,3-tetramethylbutyl)    phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.-   1.9. Aromatic hydroxybenzyl compounds, for example    1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,    1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,    2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.-   1.10. Triazine compounds, for example    2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,    2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,    2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,    2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,    1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate,    1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,    2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,    1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine,    1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.-   1.11. Benzylphosphonates, for example    dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,    diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,    dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,    dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the    calcium salt of the monoethyl ester of    3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.-   1.12. Acylaminophenols, for example 4-hydroxylauranilide,    4-hydroxystearanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)    carbamate.-   1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid    with mono- or polyhydric alcohols, e.g. with methanol, ethanol,    n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,    ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene    glycol, diethylene glycol, triethylene glycol, pentaerythritol,    tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl) oxamide,    3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,    trimethylolpropane,    4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.-   1.14. Esters of D-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic    acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol,    n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,    ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene    glycol, diethylene glycol, triethylene glycol, pentaerythritol,    tris(hydroxyethyl)isocyanurate, N,N′-bis-(hydroxyethyl) oxamide,    3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,    trimethylolpropane,    4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane;    3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)    propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]-undecane.-   1.15. Esters of D-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid    with mono- or polyhydric alcohols, e.g. with methanol, ethanol,    octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene    glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol,    diethylene glycol, triethylene glycol, pentaerythritol,    tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,    3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,    trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo    [2.2.2]octane.-   1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with    mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,    octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,    1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene    glycol, triethylene glycol, pentaerythritol,    tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,    3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,    trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo    [2.2.2]octane.-   1.17. Amides of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid    e.g. N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)    hexamethylenediamide,    N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)    trimethylenediamide,    N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide,    N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide    (Naugard®XL-1, supplied by Uniroyal).-   1.18. Ascorbic acid (vitamin C)-   1.19. Aminic antioxidants, for example    N,N′-di-isopropyl-p-phenylenediamine,    N,N′-di-sec-butyl-p-phenylenediamine,    N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,    N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,    N,N′-bis(1-methylheptyl)-p-phenylenediamine,    N,N′-dicyclohexyl-p-phenylenediamine,    N,N′-diphenyl-p-phenylenediamine,    N,N′-bis(2-naphthyl)-p-phenylenediamine,    N-isopropyl-N′-phenyl-p-phenylenediamine,    N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,    N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,    N-cyclohexyl-N′-phenyl-p-phenylenediamine,    4-(p-toluenesulfamoyl)diphenylamine,    N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine,    N-allyldiphenylamine, 4-isopropoxydiphenylamine,    N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,    N-phenyl-2-naphthylamine, octylated diphenylamine, for example    p,p′-di-tert-octyldiphenylamine, 4-n-butylaminophenol,    4-butyrylaminophenol, 4-nonanoylaminophenol,    4-dodecanoylaminophenol, 4-octadecanoylaminophenol,    bis(4-methoxyphenyl)amine,    2,6-di-tert-butyl-4-dimethylaminomethylphenol,    2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,    N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane,    1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino) propane,    (o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine,    tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and    dialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono-    and dialkylated nonyldiphenylamines, a mixture of mono- and    dialkylated dodecyldiphenylamines, a mixture of mono- and    dialkylated isopropyl/isohexyldiphenylamines, a mixture of mono- and    dialkylated tert-butyldiphenylamines,    2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a    mixture of mono- and dialkylated    tert-butyl/tert-octylphenothiazines, a mixture of mono- and    dialkylated tert-octylphenothiazines, N-allylphenothiazine,    N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene.-   2. UV absorbers and light stabilizers-   2.1. 2-(2′-Hydroxyphenyl)benzotriazoles, for example    2-(2′-hydroxy-5′-methylphenyl)benzotriazole,    2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole,    2-(5′-tert-butyl-2′-hydroxyphenyl) benzotriazole,    2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,    2-(3′,5′-di-tert-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole,    2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chlorobenzotriazole,    2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,    2-(2′-hydroxy-4′-octyloxyphenyl) benzotriazole,    2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)benzotriazole,    2-(3′,5′-bis(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole,    2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)    phenyl)-5-chlorobenzotriazole,    2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)    carbonylethyl]-2′-hydroxyphenyl)-5-chlorobenzotriazole,    2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)    phenyl)-5-chlorobenzotriazole,    2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)    phenyl)benzotriazole,    2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)    phenyl)benzotriazole,    2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)    benzotriazole,    2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole,    2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)    phenylbenzotriazole,    2,2′-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol];    the transesterification product of    2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazole    with polyethylene glycol 300; [R-CH₂CH₂—COO—CH₂CH₂—]₂, where    R=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl,    2-[2′-hydroxy-3′-(α,α-dimethylbenzyl)-5′-(1,1,3,3-tetramethylbutyl)phenyl]benzotriazole;    2-[2′-hydroxy-3′-(1,1,3,3-tetramethylbutyl)-5′-(α,α-dimethylbenzyl)phenyl]benzotriazole.-   2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy,    4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy,    4,2′,4′-trihydroxy and 2′-hydroxy-4,4′-dimethoxy derivatives.-   2.3. Esters of substituted and unsubstituted benzoic acids, for    example 4-tert-butylphenyl salicylate, phenyl salicylate,    octylphenyl salicylate, dibenzoyl resorcinol,    bis(4-tert-butylbenzoyl) resorcinol, benzoyl resorcinol,    2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate,    hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl    3,5-di-tert-butyl-4-hydroxybenzoate,    2-methyl-4,6-di-tert-butylphenyl    3,5-di-tert-butyl-4-hydroxybenzoate.-   2.4. Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate,    isooctyl α-cyano-β,β-diphenylacrylate, methyl    α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate,    butyl α-cyano-β-methyl-p-methoxycinnamate, methyl    α-carbomethoxy-p-methoxycinnamate and    N-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.-   2.5. Nickel compounds, for example nickel complexes of    2,2′-thiobis[4-(1,1,3,3-tetramethylbutyl) phenol], such as the 1:1    or 1:2 complex, with or without additional ligands such as    n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel    dibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g.    the methyl or ethyl ester, of    4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complexes    of ketoximes, e.g. of 2-hydroxy-4-methylphenylundecylketoxime,    nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or    without additional ligands.-   2.6. Sterically hindered amines, for example    bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,    bis(2,2,6,6-tetramethyl-4-piperidyl)succinate,    bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,    bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate,    bis(1,2,2,6,6-pentamethyl-4-piperidyl)    n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of    1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and    succinic acid, linear or cyclic condensates of    N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and    4-tert-octylamino-2,6-dichloro-1,3,5-triazine,    tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,    tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate,    1,1′-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone),    4-benzoyl-2,2,6,6-tetramethylpiperidine,    4-stearyloxy-2,2,6,6-tetramethylpiperidine,    bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,    3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,    bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate,    bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, linear or    cyclic condensates of    N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and    4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of    2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine    and 1,2-bis(3-aminopropylamino)ethane, the condensate of    2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazine    and 1,2-bis(3-aminopropylamino)ethane,    8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro    [4.5]decane-2,4-dione,    3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione,    3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione,    a mixture of 4-hexadecyloxy- and    4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensate of    N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and    4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensate of    1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine    as well as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.    [136504-96-6]); a condensate of 1,6-hexanediamine and    2,4,6-trichloro-1,3,5-triazine as well as N,N-dibutylamine and    4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.    [192268-64-7]);    N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide,    N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide,    2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro    [4,5]decane, a reaction product of    7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro-[4,5]decane    and epichlorohydrin,    1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)    ethene, N,N′-bis-formyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)    hexamethylenediamine, a diester of 4-methoxymethylenemalonic acid    with 1,2,2,6,6-pentamethyl-4-hydroxypiperidine,    poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane,    a reaction product of maleic acid anhydride-α-olefin copolymer with    2,2,6,6-tetramethyl-4-aminopiperidine or    1,2,2,6,6-pentamethyl-4-aminopiperidine.-   2.7. Oxamides, for example 4,4′-dioctyloxyoxanilide,    2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide,    2,2′-didodecyloxy-5,5′-di-tert-butoxanilide,    2-ethoxy-2′-ethyloxanilide, N,N′-bis(3-dimethylaminopropyl)oxamide,    2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with    2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- and    p-methoxy-disubstituted oxanilides and mixtures of o- and    p-ethoxy-disubstituted oxanilides.-   2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example    2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,    2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,    2-(2,4-dihydroxyphenyl)-4,6-bis (2,4-dimethylphenyl)-1,3,5-triazine,    2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,    2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,    2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,    2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,    2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,    2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)    phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,    2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis    (2,4-dimethylphenyl)-1,3,5-triazine,    2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,    2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,    2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,    2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy) phenyl]-1    ,3,5-triazine,    2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine,    2-(2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.-   3. Metal deactivators, for example N,N′-diphenyloxamide,    N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl)hydrazine,    N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine,    3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl    dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl    bisphenylhydrazide, N,N′-diacetyladipoyl dihydrazide,    N,N′-bis(salicyloyl) oxalyl dihydrazide,    N,N′-bis(salicyloyl)thiopropionyl dihydrazide.-   4. Phosphites and phosphonites, for example triphenyl phosphite,    diphenylalkyl phosphites, phenyldialkyl phosphites,    tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl    phosphite, distearylpentaerythritol diphosphite,    tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol    diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol    diphosphite, bis(2,4-dicumylphenyl) pentaerythritol diphosphite,    bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite,    diisodecyloxypentaerythritol diphosphite,    bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite,    bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite,    tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)    4,4′-biphenylene diphosphonite,    6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz    [d,g]-1,3,2-dioxaphosphocin, bis(2,4-di-tert-butyl-6-methylphenyl)    methyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl    phosphite,    6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin,    2,2′,2″-nitrilo[triethyltris    (3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite],    2-ethylhexyl(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)    phosphite,    5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane.-   5. Hydroxylamines, for example N,N-dibenzylhydroxylamine,    N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,    N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,    N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,    N-hexadecyl-N-octadecylhydroxylamine,    N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine    derived from hydrogenated tallow amine.-   6. Nitrones, for example N-benzyl-alpha-phenylnitrone,    N-ethyl-alpha-methyinitrone, N-octyl-alpha-heptylnitrone,    N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnitrone,    N-hexadecyl-alpha-pentadecylnitrone,    N-octadecyl-alpha-heptadecylnitrone,    N-hexadecyl-alpha-heptadecylnitrone,    N-ocatadecyl-alpha-pentadecylnitrone,    N-heptadecyl-alpha-heptadecyinitrone,    N-octadecyl-alpha-hexadecylnitrone, nitrone derived from    N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.-   7. Thiosynergists, for example dilauryl thiodipropionate or    distearyl thiodipropionate.-   8. Peroxide scavengers, for example esters of β-thiodipropionic    acid, for example the lauryl, stearyl, myristyl or tridecyl esters,    mercaptobenzimidazole or the zinc salt of 2-mercapto-benzimidazole,    zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol    tetrakis(β-dodecylmercapto) propionate.-   9. Polyamide stabilisers, for example copper salts in combination    with iodides and/or phosphorus compounds and salts of divalent    manganese.-   10. Basic co-stabilisers, for example melamine,    polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea    derivatives, hydrazine derivatives, amines, polyamides,    polyurethanes, alkali metal salts and alkaline earth metal salts of    higher fatty acids, for example calcium stearate, zinc stearate,    magnesium behenate, magnesium stearate, sodium ricinoleate and    potassium palmitate, antimony pyrocatecholate or zinc    pyrocatecholate.-   11. Nucleating agents, for example inorganic substances, such as    talcum, metal oxides, such as titanium dioxide or magnesium oxide,    phosphates, carbonates or sulfates of, preferably, alkaline earth    metals; organic compounds, such as mono- or polycarboxylic acids and    the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid,    diphenylacetic acid, sodium succinate or sodium benzoate; polymeric    compounds, such as ionic copolymers (ionomers). Especially preferred    are 1,3:2,4-bis(3′,4′-dimethylbenzylidene)sorbitol,    1,3:2,4-di(paramethyldibenzylidene) sorbitol, and    1,3:2,4-di(benzylidene)sorbitol.-   12. Fillers and reinforcing agents, for example calcium carbonate,    silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica,    barium sulfate, metal oxides and hydroxides, carbon black, graphite,    wood flour and flours or fibers of other natural products, synthetic    fibers.-   13. Other additives, for example plasticisers, lubricants,    emulsifiers, pigments, rheology additives, catalysts, flow-control    agents, optical brighteners, flameproofing agents, antistatic agents    and blowing agents.-   14. Benzofuranones and indolinones, for example those disclosed in    U.S. Pat. No. 4,325,863; U.S. Pat. No. 4,338,244; U.S. Pat. No.    5,175,312; U.S. Pat. No. 5,216,052; U.S. 5,252,643; DE-A-4316611;    DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102 or    3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butylbenzofuran-2-one,    5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,    3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],    5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,    3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one,    3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butylbenzofuran-2-one,    3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one,    3-(2,3-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one.

The additives are added, for example, in concentrations of 0.01 to 10%,relative to the total weight of the carrier.

Preferred further additives are phenolic antioxidants, light-stabilizersand/or processing stabilizers.

Incorporation of the compounds of the formula I and, if desired, furtheradditives into the synthetic polymers is carried out by known methods,for example before or during moulding or else by applying the dissolvedor dispersed compounds to the synthetic polymer, if appropriate withsubsequent slow evaporation of the solvent. The compounds of the formulaI can also be added to the synthetic polymers in the form of amasterbatch containing them, for example, in a concentration of 2.5 to25% by weight.

The compounds of the formula I can be incorporated into syntheticpolymers at high temperature processing condition.

The compounds of the formula I, with or without further additives, canbe incorporated in pure form or encapsulated in waxes, oils or polymersinto the synthetic polymer.

The compounds of the formula I, with or without further additives, canalso be sprayed onto the synthetic polymer. It is able to dilute otheradditives (for example the conventional additives indicated above) ortheir melts so that they too can be sprayed together with theseadditives onto the polymer.

In the case of spherically polymerized polyolefins it may, for example,be advantageous to apply the compounds of the formula I, with or withoutother additives, by spraying.

The materials treated in this way can be employed in a wide variety offorms, for example as foams, films, fibres, tapes, moulding compositionsor as binders for coating materials.

The present invention also relates to new compounds of the formula I

wherein

-   -   R₁ is C₁-C₂₅alkyl, C₂-C₂₅alkenyl, C₂-C₂₅alkynyl, unsubstituted        or C₁-C₄alkyl-substituted phenyl; C₇-C₉phenylalkyl,        unsubstituted or C₁-C₄alkyl-substituted C₅-C₈cycloalkyl;    -   R₂, R₃ and R₄ are each independently of the others    -   R₅ is C₁-C₁₈alkylene, C₂-C₁₈alkylene which is interrupted by        oxygen; C₂-C₁₈alkenylene, C₂-C₂₀alkylidene,        C₇-C₂₀phenylalkylidene, C₅-C₈cycloalkylene, unsubstituted or        C₁-C₄alkyl-substituted phenylene,    -   R₆ and R₇ are each independently of one another hydrogen or        C₁-C₈alkyl,    -   R₈ is unsubstituted or C₁-C₄alkyl-substituted C₂-C₁₂alkylene;    -   R₉ is C₁-C₂₅alkyl, C₂-C₂₅alkyl interrupted by oxygen;        C₇-C₉phenylalkyl, unsubstituted or C₁-C₄alkyl-substituted        C₅-C₈cycloalkyl; unsubstituted or C₁-C₄alkyl-substituted phenyl;        and    -   n is 1.

Of interest are the new compounds of the formula I wherein

-   -   R₁ is C₁-C₂₅alkyl, C₂-C₂₅alkenyl, C₃-C₂₅alkynyl, unsubstituted        or C₁-C₄alkyl-substituted phenyl; C₇-C₉phenylalkyl,        unsubstituted or C₁-C₄alkyl-substituted C₅-C₈cycloalkyl.

Of special interest are the new compounds of the formula I wherein

-   -   R₁ is C₁₀-C₁₂alkyl,    -   R₂, R₃ and R₄ are each independently of the others    -   R₅ is C₂-C₄alkylene,    -   R₆ and R₇ are each independently of one another methyl or ethyl,        and    -   n is 1.

The present invention also relates to a method of protecting acorrodible metal substrate, which comprises applying to this substrate acomposition comprising a component (a) and (b).

A preferred embodiment of the present invention is therefore the use ofa compound of the formula I as corrosion inhibitor in carriers forprotecting metallic surfaces.

The following Examples illustrate the invention further. Parts orpercentages relate to weight.

EXAMPLE 1 Preparation of Compound 101

a) Preparation of Trichlorododecylsilane with 1-dodecene andTrichlorosilane.

In a round bottomed flask 60 g of freshly distilled 1-dodecene istreated with 3 ml of a 2% solution of hexachloroplatinic acid [H₂PtCl₆]in isopropanol and stirred for 30 minutes at room temperature. Thesolution is warmed to 40-45° C. and then added 62.7 g (30% excess) oftrichlorosilane. The exothermic reaction is maintained at 55-65° C. andstirred for another hour. Distillation under reduced pressure (boilingpoint 115- 120° C. at 1 mbar) gives 90 g of trichlorododecylsilane,colorless oil.

b) Preparation of Compound (101).

To a solution of 87.5 g of N,N-diethylaminoethanol and 120 mltriethylamine in 250 g of toluene is added 60 g oftrichlorododecylsilane [prepared according to Example 1a] controllingthe exothermic reaction at the temperature range of 65-70° C. Thereaction mixture is maintained at 70° C. for 4 hours. The reactionmixture is cooled to room temperature, filtered and the filtrateconcentrated using a vacuum rotary evaporator. Distillation underreduced pressure (boiling point 220° C. at 0.1 mbar) gives 70 g ofcompound (101), yellow, viscous oil.

EXAMPLE 2 Preparation of Compound (102)

In analogy to Example 1b starting from dichlorododecylmethylsilane[prepared in analogy to Example 1a starting from dichloromethylsilaneinstead of trichlorosilane] instead of trichlorododecylsilane, compound(102), b.p. 180-185° C. at 0.4 mbar, is obtained.

EXAMPLE 3 Preparation of Compound 103

In analogy to Example 1b starting from chlorododecyldimethylsilane[prepared in analogy to Example 1a starting from chlorodimethylsilaneinstead of trichlorosilane] instead of trichlorododecylsilane, compound(103), colorless oil, is obtained.

NMR [300 MHz, CDCl₃, δ (ppm)]: 3.61 (t, 2 H); 2.53 (m, 6 H); 1.23 (m, 20H); 0.98 (t, 6 H); 0.87 (t, 3 H); 0.55 (t, 2 H); 0.073 (s, 6 H).

EXAMPLE 4 Preparation of Compound (104)

In analogy to Example 1b starting from dichlorodimethylsilane instead oftrichlorododecylsilane, compound (104), colorless oil, b.p. 110-113° C.at 3 mbar, is obtained.

EXAMPLE 5 Preparation of Compound (105)

Compound (105) is obtained by transetherification of tetraethoxysilanewith N,N-diethylaminoethanol without solvent at 130° C. withdibutyltinoxide as catalyst. B.p. 162-166° C. at 0.3 mbar.

EXAMPLE 6 Preparation of Compound (106)

In analogy to Example 1b starting from trichlorophenylsilane instead oftrichlorododecylsilane, compound (106), colorless oil, b.p. 190-195° C.at 1 mbar, is obtained.

EXAMPLE 7 Preparation of Compound (107)

In analogy to Example 1b starting from dichlorodiphenylsilane instead oftrichlorododecylsilane, compound (107), yellow oil, b.p. 165- 170° C. at1 mbar, is obtained.

EXAMPLE 8 Preparation of Compound (108)

In analogy to Example 1b starting from 2-piperidin-1-yl-ethanol insteadof N,N-diethylaminoethanol, compound (108), orange oil, is obtained.

NMR [300 MHz, CDCl₃, δ (ppm)]: 3.84 (t, 6 H); 2.47 (t, 6 H); 2.39 (t, 12H); 1.54-1.37 (m, 18 H); 1.21 (m, 20 H); 0.83 (t, 3 H); 0.61 (t, 2 H).

EXAMPLE 9 Preparation of Compound (109)

In analogy to Example 1b starting from 1,8-bis(trichlorosilyl)octane[prepared in analogy to Example 1a starting from 1,7-octadiene insteadof 1-dodecene] instead of trichlorododecylsilane, compound (109), orangeoil, is obtained.

NMR [300 MHz, CDCl₃, δ (ppm)]: 3.74 (t, 12 H); 2.54 (m, 36 H); 1.21 (m,12 H); 0.97 (m, 36 H); 0.57 (t, 4 H).

EXAMPLE 10 Preparation of Compound (110)

In analogy to Example 1b starting from silane,[(1-methylethylidene)bis(1,4-phenylenoxy-1,3-propanediyl)]bis[trichloro]instead of trichlorododecylsilane, compound (110) is obtained.

NMR [300 MHz, CDCl₃, δ (ppm)]: 7.06 (dd, 8 H); 3.79 (m, 16 H); 2.55 (m,36 H); 1.91 (m, 4 H); 1.59 (s, 6 H); 0.99 (t, 36 H); 0.80 (t, 4 H).

EXAMPLE 11 Preparation of Compound (111)

To a solution of 2 mol N,N-diethylaminoethanol, 1 mol 2-phenylethanoland 120 ml triethylamine in 250 g of toluene is added 1 mol oftrichlorbphenylsilane controlling the exothermic reaction at thetemperature range of 65-70° C. The reaction mixture is maintained at 70°C. for 4 hours. The reaction mixture is cooled to room temperature,filtered and the filtrate concentrated using a vacuum rotary evaporator.Distillation under reduced pressure gives mainly compound (111).

NMR [300 MHz, CDCl₃, δ (ppm)]: 7.3-7.1 (m, 10 H); 4.0-3.8 (m, 6 H); 2.87(m, 2 H); 2.6-2.5 (m, 12 H); 0.99 (m, 12 H).

EXAMPLE 12 Preparation of Compound (112)

In analogy to Example 1b starting from propargyl alcohol instead ofN,N-diethylaminoethanol, compound (112), b.p. 130-135° C. at 1 mbar, isobtained.

EXAMPLE 13 Corrosion Inhibition

The corrosion inhibiting ability of the products is assessed accordingto the FED.TEST METHOD STD. NO. 101C procedure A: Ten milliliters ofglycerin-water solution having a specific gravity of about 1.074 atambient temperature to affect an atmosphere of about 85 percent relativehumidity is introduced into the bottom of the test assembly. 0.05±0.005g of the compounds of the instant invention is introduced in the testassembly in a small vessel placed on the bottom of the jar. The lid isclosed tightly. The test assembly is exposed for 20 hours at 24° C.Then, cold water at 0° C. is added to the aluminum tube until full.After 3 hours, the water is removed from the tube and the steel specimenis evaluated for any evidences of corrosion. This test is carried out on3 test pieces for 8 cycles and on a blank test at the same time. Avisual corrosion evaluation is assessed according to the followingrating: “none” means no corrosion; “very low” means very low corrosion;“low” means low corrosion; and “high” means high corrosion. The resultsare summarized in Table 1. TABLE 1 Visual corrosion Example Corrosioninhibitor Piece 1 Piece 2 Piece 3 13a^(a)) Blank (1 cycle) high highhigh 13b^(b)) Compound 101 (8 cycles) none none none 13c^(b)) Compound102 (8 cycles) none none none 13d^(b)) Compound 103 (8 cycles) none nonenone 13e^(b)) Compound 104 (8 cycles) none none none 13f^(b)) Compound106 (8 cycles) none none none 13g^(b)) Compound 107 (8 cycles) none nonenone 13h^(b)) Compound 108 (8 cycles) none none none 13i^(b)) Compound109 (8 cycles) none none none 13j^(b)) Compound 110 (8 cycles) none nonenone 13k^(b)) Compound 111 (8 cycles) none none none^(a))Comparison example.^(b))Example according to the invention.

EXAMPLE 14 Corrosion Inhibition with a Polyethylene Powder Carrier

20 g of the compounds of the instant invention is mixed in a turbo mixerwith 1000 g of a low density polyethylene [Riblene FF29 (RTM) powder(Polimeri Europa)] having a melt index of 0.6 g/10 min. (measured at190° C. and 2.16 kg). The mixture is extruded at a maximum temperatureof 170° C. using an O.M.C. extruder, to give polymer granules which aresubsequently grinded to obtain a powder. 2.5 g of this powder is placedinto the vessel of the test assembly and its corrosion inhibitingability is assessed according to the afore mentioned FED.TEST METHODSTD. NO. 101C procedure A according to Example 13 (with 2.5 g of thepowder instead of 0.05 g). The test is carried out on 3 test pieces for8 cycles and on a blank test at the same time. The results obtained aresummarized in Table 2 and compared to a blank test after 1 cycle. TABLE2 Visual corrosion Example Corrosion inhibitor Piece 1 Piece 2 Piece 314a^(a)) Blank (1 cycle) high high high 14b^(b)) 2% compound 107 (8cycles) none none none^(a))Comparison example.^(b))Example according to the invention.

EXAMPLE 15 Corrosion Inhibition with a Polyethylene Film Carrier

20 g of the compounds of the instant invention is mixed in a turbo mixerwith 1000 g of a low density polyethylene [Riblene FF29 (RTM) powder(Polimeri Europa)] having a melt index of 0.6 g/10 min. (measured at190° C. and 2.16 kg). The mixture is extruded at a maximum temperatureof 170° C. using an O.M.C. extruder, to give polymer granules which aresubsequently converted to a film of 100 μm thickness, using ablow-extruder (Formac) and working at a maximum temperature of 210° C.Part of this film is grinded to obtain a powder. 2.5 g of this powder isplaced into the vessel of the test assembly and its corrosion inhibitingability is assessed according to the afore mentioned FED.TEST METHODSTD. NO. 101C procedure A according to Example 13 (with 2.5 g of thepowder instead of 0.05 g). The test is carried out on 3 test pieces for8 cycles and on a blank test at the same time. The results obtained aresummarized in Table 3 and compared to a blank test after 1 cycle. TABLE3 Visual corrosion Example Corrosion inhibitor Piece 1 Piece 2 Piece 315a^(a)) Blank (1 cycle) high high High 15b^(b)) 2% compound 101 (8cycles) none none None^(a))Comparison example.^(b))Example according to the invention.

Additionally, the corrosion inhibiting ability of the obtained film isassessed according to the FED.TEST METHOD STD. NO. 101C procedure B: Tenmilliliters of glycerin-water solution having a specific gravity ofabout 1.074 at ambient temperature to affect an atmosphere of about 85percent relative humidity is introduced into the bottom of the testassembly. Two specimens are placed through the parallel slots of thetest assembly jar. To fasten the film in position, a part of thespecimen is bent onto the outer surface of the lid and this tab and theslot covered with tape having a low water vapor transmission rate. Thelid is closed tightly. The test assembly is exposed for 20 hours at 24°C. Then, cold water at 0° C. is added to the aluminum tube until full:After 3 hours, the water is removed from the tube and the steel specimenis evaluated for any evidences of corrosion. This test is carried out on3 test pieces and on a blank test at the same time. A visual corrosionevaluation is assessed according to the rating used in procedure A. Theresults are summarized in Table 4. TABLE 4 Visual corrosion ExampleCorrosion inhibitor Piece 1 Piece 2 Piece 3 15c^(a)) Blank (1 cycle)high high High 15d^(b)) 2% compound 101 (1 cycle) low low low^(a))Comparison example.^(b))Example according to the invention.

1. A composition comprising a) a carrier, and b) as corrosion inhibitorat least one compound of the formula I

wherein, when n is 1, R₁ is hydrogen, C₁-C₃₂alkyl, C₂-C₃₂alkenyl,C₂-C₃₂alkynyl, unsubstituted or C₁-C₄alkyl-substituted phenyl;C₇-C₉phenylalkyl, C₁-C₃₂alkoxy, C₂-C₃₂alkenyloxy, C₂-C₃₂alkynyloxy,unsubstituted or C₁-C₄alkyl-substituted C₅-C₈cycloalkyl; unsubstitutedor C₁-C₄alkyl-substituted C₅-C₈cycloalkoxy;

when n is 2, R₂ is C₁-C₃₂alkylene, C₂-C₃₂alkylene interrupted by oxygen;C₅-C₈cycloalkylene or -R₁₀-O-R₁₂-O-R₁₁-, when n is 3, R₁ isC₁-C₃₂alkanetriyl,

when n is 4, R₁ is C₁-C₃₂alkanetetrayl,

R₂, R₃ and R₄ are each independently of the others C₁-C₃₂alkyl,C₂-C₃₂alkenyl, C₂-C₃₂alkynyl, unsubstituted or C₁-C₄alkyl-substitutedphenyl; C₇-C₉phenylalkyl, C₇-C₉phenylalkoxy, C₁-C₃₂alkoxy,C₂-C₃₂alkenyloxy, C₂-C₃₂alkynyloxy, unsubstituted orC₁-C₄alkyl-substituted C₅-C₈cycloalkyl; unsubstituted orC₁-C₄alkyl-substituted C₅-C₈cycloalkoxy;

at least one of the radicals R₂, R₃ or R₄ is C₂-C₃₂alkynyloxy,

R₅ is C₁-C₁₈alkylene, C₂-C₁₈alkylene which is interrupted by oxygen;C₂-C₁₈alkenylene, C₂-C₂₀alkylidene, C₇-C₂₀phenylalkylidene,C₅-C₈cycloalkylene, unsubstituted or C₁-C₄alkyl-substituted phenylene,R₆ and R₇ are each independently of one another hydrogen or C₁-C₁₂alkyl,R₈ is unsubstituted or C₁-C₄alkyl-substituted C₂-C₁₂alkylene; R₉ isC₁-C₂₅alkyl, C₂-C₂₅alkyl interrupted by oxygen; C₇-C₉phenylalkyl,unsubstituted or C₁-C₄alkyl-substituted C₅-C₈cycloalkyl; unsubstitutedor C₁-C₄alkyl-substituted phenyl; R₁₀ and R₁₁ are each independently ofone another C₁-C₁₈alkylene, C₂-C₁₈alkylene which is interrupted byoxygen; C₂-C₁₈alkenylene, C₂-C₂₀alkylidene, C₇-C₂₀phenylalkylidene,C₅-C₈cycloalkylene, unsubstituted or C₁-C₄alkyl-substituted phenylene;R₁₂ is C₁-C₁₈alkylene, C₂-C₁₈alkylene which is interrupted by oxygen;C₂-C₁₈alkenylene, C₂-C₂₀alkylidene, C₇-C₂₀phenylalkylidene,C₅-C₈cycloalkylene, unsubstituted or C₁-C₄alkyl-substituted phenylene;unsubstituted or C₁-C₄alkyl-substituted naphthylene; or

R₁₃, R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, R₁₉, R₂₀, R₂₁, R₂₂, R₂₃and R₂₄are eachindependently of the others C₁-C₁₈alkylene, C₂-C₁₈alkylene which isinterrupted by oxygen; C₂-C₁₈alkenylene, C₂-C₂₀alkylidene,C₇-C₂₀phenylalkylidene, C₅-C₈cycloalkylene, unsubstituted orC₁-C₄alkyl-substituted phenylene; R₂₅ and R₂₆ are each independently ofone another hydrogen, CF₃, C₁-C₁₂alkyl or phenyl, or R₂₅ and R₂₆together with the linking carbon atom, form a C₅-C₈cycloalkylidene ringwhich is unsubstituted or substituted by 1 to 3 C₁-C₄alkyl groups; R₂₇,R₂₈, R₂₉ and R₃₀ are each independently of the others hydrogen orC₁-C₈alkyl; and n is 1, 2, 3 or4.
 2. A composition according to claim 1,wherein, when n is 1, R₁ is hydrogen, C₁-C₃₂alkyl, C₂-C₃₂alkenyl,C₃-C₃₂alkynyl, unsubstituted or C₁-C₄alkyl-substituted phenyl;C₇-C₉phenylalkyl, C₁-C₃₂alkoxy, C₂-C₃₂alkenyloxy, C₂-C₃₂alkynyloxy,unsubstituted or C₁-C₄alkyl-substituted C₅-C₈cycloalkyl; unsubstitutedor C₁-C₄alkyl-substituted C₅-C₈cycloalkoxy;

when n is 2, R₁ is C₁-C₃₂alkylene, C₂-C₁₈alkylene interrupted by oxygen;C₅-C₈cycloalkylene or -R₁₀-O-R₁₂-O-R₁₁-, when n is 3, R₁ isC₁-C₃₂alkanetriyl,

when n is 4, R₁ is C₁-C₃₂alkanetetrayl,

R₂, R₃ and R₄ are each independently of the others C₁-C₃₂alkyl,C₂-C₃₂alkenyl, C₃-C₃₂alkynyl, unsubstituted or C₁-C₄alkyl-substitutedphenyl; C₇-C₉phenylalkyl, C₇-C₉phenylalkoxy, C₁-C₃₂-alkoxy,C₂-C₃₂alkenyloxy, C₂-C₃₂alkynyloxy, unsubstituted orC₁-C₄alkyl-substituted C₅-C₈cycloalkyl; unsubstituted orC₁-C₄alkyl-substituted C₅-C₈cycloalkoxy;

with the proviso that at least one of the radicals R₂, R₃ or R₄ isC₂-C₃₂alkynyloxy,

R₅ is C₁-C₁₈alkylene, C₂-C₁₈alkylene which is interrupted by oxygen;C₂-C₁₈alkenylene, C₂-C₂₀alkylidene, C₇-C₂₀phenylalkylidene,C₅-C₈cycloalkylene, unsubstituted or C₁-C₄alkyl-substituted phenylene,R₆ and R₇ are each independently of one another hydrogen or C₁-C₁₂alkyl,R₈ is unsubstituted or C₁-C₄alkyl-substituted C₂-C₁₂alkylene; R₉ isC₁-C₂₅alkyl, C₂-C₂₅alkyl interrupted by oxygen; C₇-C₉phenylalkyl,unsubstituted or C₁-C₄alkyl-substituted C₅-C₈cycloalkyl; unsubstitutedor Cl-C₄alkyl-substituted phenyl; R₁₀ and R₁₁ are each independently ofone another C₁-C₁₈alkylene, C₂-C₁₈alkylene which is interrupted byoxygen; C₂-C₁₈alkenylene, C₂-C₂₀alkylidene, C₇-C₂₀phenylalkylidene,C₅-C₈-cycloalkylene, unsubstituted or C₁-C₄alkyl-substituted phenylene;R₁₂ is C₁-C₁₈alkylene, C₂-C₁₈alkylene which is interrupted by oxygen;C₂-C₁₈alkenylene, C₂-C₂₀alkylidene, C₇-C₂₀phenylalkylidene,C₅-C₈cycloalkylene, unsubstituted or C₁-C₄alkyl-substituted phenylene;unsubstituted or C₁-C₄alkyl-substituted naphthylene; or

R₁₃, R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, R₁₉ , R₂₀, R₂₁, R₂₂, R₂₃ and R₂₄ are eachindependently of the others C₁-C₁₈alkylene, C₂-C₁₈alkylene which isinterrupted by oxygen; C₂-C₁₈alkenylene, C₂-C₂₀alkylidene,C₇-C₂₀phenylalkylidene, C₅-C₈cycloalkylene, unsubstituted orC₁-C₄alkyl-substituted phenylene; R₂₅ and R₂₆ are each independently ofone another hydrogen, CF₃, C₁-C₁₂alkyl or phenyl, or R₂₅ and R₂₆together with the linking carbon atom, form a C₅-C₈cycloalkylidene ringwhich is unsubstituted or substituted by 1 to 3 C₁-C₄alkyl groups; R₂₇is hydrogen or C₁-C₈alkyl; and n is 1, 2, 3 or
 4. 3. A compositionaccording to claim 1, wherein, when n is 1, R₁ is hydrogen, C₁-C₁₈alkyl,C₂-C₁₈alkenyl, C₃-C₁₈alkynyl, unsubstituted or C₁-C₄alkyl-substitutedphenyl; C₇-C₉phenylalkyl, C₁-C₁₈alkoxy, C₂-C₁₈alkenyloxy,C₂-C₁₈alkynyloxy, unsubstituted or C₁-C₄alkyl-substitutedC₅-C₈cycloalkyl; unsubstituted or C₁-C₄alkyl-substitutedC₅-C₈cycloalkoxy;

when n is 2, R₁ is C₁-C₁₈alkylene, C₄-C₁₈alkylene interrupted by oxygen;C₅-C₇cycloalkylene or -R₁₀-O-R₁₂-O-R₁₁-, when n is 3, R₁ isC₁-C₁₈alkanetriyl or

when n is 4, R₁ is C₁-C₁₈alkanetetrayl,

R₂, R₃ and R₄ are each independently of the others C₁-C₁₈alkyl,C₂-C₁₈alkenyl, C₃-C₁₈alkynyl, unsubstituted or C₁-C₄alkyl-substitutedphenyl; C₇-C₉phenylalkyl, C₇-C₉phenylalkoxy, C₁-C₁₈alkoxy,C₂-C₁₈alkenyloxy, C₂-C₁₈alkynyloxy, unsubstituted orC₁-C₄alkyl-substituted C₅-C₈cycloalkyl; unsubstituted orC₁-C₄alkyl-substituted C₅-C₈cycloalkoxy;

with the proviso that at least one of the radicals R₂, R₃ or R₄ isC₂-C₁₈alkynyloxy,

R₅ is C₁-C₁₂alkylene, C₄-C₁₂alkylene which is interrupted by oxygen;C₂-C₁₂alkenylene, C₂-C₁₂alkylidene, C₇-C₁₂phenylalkylidene,C₅-C₈cycloalkylene, unsubstituted or C₁-C₄alkyl-substituted phenylene,R₆ and R₇ are each independently of one another hydrogen or C₁-C₈alkyl,R₈ is unsubstituted or C₁-C₄alkyl-substituted C₂-C₈alkylene; R₉ isC₁-C₁₈alkyl, C₄-C₁₈alkyl interrupted by oxygen; C₇-C₉phenylalkyl,unsubstituted or C₁-C₄alkyl-substituted C₅-C₈cycloalkyl; unsubstitutedor C₁-C₄alkyl-substituted phenyl; R₁₀ and R₁₁ are each independently ofone another C₁-C₁₂alkylene, C₄-C₁₈alkylene which is interrupted byoxygen; C₂-C₁₈alkenylene, C₂-C₁₂alkylidene, C₇-C₁₂phenylalkylidene,C₅-C₈cycloalkylene, unsubstituted or C₁-C₄alkyl-substituted phenylene;R₁₂ is C₁-C₁₈alkylene, C₄-C₁₈alkylene which is interrupted by oxygen;C₂-C₁₈alkenylene, C₂-C₁₂alkylidene, C₇-C₁₂phenylalkylidene,C₅-C₈cycloalkylene, unsubstituted or C₁-C₄alkyl-substituted phenylene;unsubstituted or C₁-C₄alkyl-substituted naphthylene; or

R₁₃, R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, R₁₉ , R₂₀, R₂₁, R₂₂, R₂₃ and R₂₄ are eachindependently of the others C₁-C₁₈alkylene, C₄-C₁₈alkylene which isinterrupted by oxygen; C₂-C₁₈alkenylene, C₂-C₁₂alkylidene,C₇-C₁₂phenylalkylidene, C₅-C₈cycloalkylene, unsubstituted orC₁-C₄alkyl-substituted phenylene; R₂₅ and R₂₆ are each independently ofone another hydrogen, CF₃, C₁-C₁₂alkyl or phenyl, or R₂₅ and R₂₆together with the linking carbon atom, form a C₅-C₈cycloalkylidene ringwhich is unsubstituted or substituted by 1 to 3 C₁-C₄alkyl groups; and nis 1, 2, 3 or
 4. 4. A composition according to claim 1, wherein n is 1or
 2. 5. A composition according to claim 1, wherein at least one of theradicals R₂, R₃ or R₄ is C₃-C₄alkynyloxy,

R₅ is C₁-C₁₂alkylene, C₄-C₁₂alkylene which is interrupted by oxygen; orC₂-C₁₂alkenylene, R₆ and R₇ are each independently of one anotherC₁-C₄alkyl, and R₈ is C₄-C₆alkylene.
 6. A composition according to claim1, wherein, when n is 1, R₁ is C₁-C₁₈alkyl, C₂-C₈alkenyl, C₃-C₈alkynyl,phenyl; benzyl, C₁-C₁₂alkoxy, C₂-C₁₂alkenyloxy, C₂-C₁₂alkynyloxy,C₅-C₈cycloalkyl, C₅-C₈cycloalkoxy,

when n is 2, R₁ is C₂-C₁₈alkylene, C₄-C₁₈alkylene interrupted by oxygen;or -R₁₀-O-R₁₂-O-R₁₁-, when n is 3, R₁ is C₄-C₁₂alkanetriyl or

when n is 4, R₁ is C₅-C₁₂alkanetetrayl,

R₂, R₃ and R₄ are each independently of the others C₁-C₈alkyl,C₂-C₈alkenyl, C₃-C₈alkynyl, phenyl; benzyl, phenylethoxy, C₁-C₁₂alkoxy,C₃-C₁₂alkenyloxy, C₃-C₁₂alkynyloxy, C₅-C₈cycloalkyl, C₅-C₈cycloalkoxy,

or; with the proviso that at least one of the radicals R₂, R₃ or R₄ isC₃-C₁₂alkynyloxy,

R₅ is C₂-C₈alkylene, C₄-C₈alkylene which is interrupted by oxygen;C₄-C₈alkenylene, C₂-C₈alkylidene, benzylidene, cyclohexylene orphenylene, R₆ and R₇ are each independently of one another C₁-C₄alkyl,R₈ is C₄-C₆alkylene, R₁₀ and R₁₁ are each independently of one anotherC₂-C₈alkylene, C₄-C₁₈alkylene which is interrupted by oxygen;C₂-C₂alkenylene, C₂-C₈alkylidene, benzylidene, cyclohexylene orphenylene, R₁₂ is C₂-C₁₂alkylene, C₄-C₁₂alkylene which is interrupted byoxygen; C₂-C₁₂alkenylene, C₂-C₈alkylidene, benzylidene, cyclohexylene,unsubstituted, phenylene, naphthylene or

R₁₃, R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, R₁₉ , R₂₀, R₂₁, R₂₂, R₂₃ and R₂₄ are eachindependently of the others C₂-C₈alkylene, C₄-C₈alkylene which isinterrupted by oxygen; C₄-C8alkenylene, C₂-C₈alkylidene, benzylidene,cyclohexylene or phenylene, R₂₅ and R₂₆ are each independently of oneanother hydrogen or C₁-C₄alkyl, or R₂₅ and R₂₆ together with the linkingcarbon atom, form a cyclohexylidene ring; and n is 1, 2, 3 or
 4. 7. Acomposition according to claim 1, wherein, when n is 1, R₁ isC₁-C₁₈alkyl, phenyl; benzyl, C₁-C₁₂alkoxy, C₃-C₆alkynyloxy,

when n is 2, R₁ is C₄-C₁₂alkylene, C₄-C₁₂alkylene interrupted by oxygen;or -R₁₀-O-R₁₂-O-R₁₁-, when n is 3, R₁ is C₄-C₈alkanetriyl, when n is 4,R₁ is C₅-C₈alkanetetrayl, R₂, R₃ and R₄ are each independently of theothers C₁-C₆alkyl, phenyl; benzyl, phenylethoxy, C₁-C₄alkoxy,C₃-C₈alkenyloxy, C₃-C₈alkynyloxy, cyclohexyl, cyclohexyloxy,

with the proviso that at least one of the radicals R₂, R₃ or R₄ isC₃-C₈alkynyloxy,

R₅ is C₂-C₈alkylene or C₄-C₈alkylene which is interrupted by oxygen; R₆and R₇ are each independently of one another C₁-C₄alkyl, R₈ isC₄-C₅alkylene, R₁₀ and R₁₁ are each independently of one anotherC₂-C₈alkylene or C₄-C₁₈alkylene which is interrupted by oxygen; R₁₂ isC₂-C₈alkylene, C₄-C₈alkylene which is interrupted by oxygen; or

R₂₅ and R₂₆ are each independently of one another hydrogen orC₁-C₄alkyl, or R₂₅ and R₂₆ together with the linking carbon atom, form acyclohexylidene ring; and n is 1, 2, 3 or
 4. 8. A composition accordingto claim 1, wherein, when n is 1, R₁ C₁-C₁₂alkyl, phenyl or

when n is 2, R₁ is C₆-C₁₀alkylene or -R₁₀-O-R₁₂-O-R₁₁, R₂, R₃ and R₄ areeach independently of the others C₁-C₃alkyl, phenyl; phenylethoxy,C₃-C₄alkynyloxy;

with the proviso that at least one of the radicals R₂, R₃ or R₄ isC₃-C₄alkynyloxy,

R₅ is C₂-C₄alkylene, R₆ and R₇ are each independently of one anothermethyl or ethyl, R₈ is C₄-C₅alkylene, R₁₀ and R₁₁ are each independentlyof one another C₂-C₄alkylene, R₁₂ is

R₂₅ and R₂₆ are each independently of one another hydrogen orC₁-C₄alkyl; and n is 1 or
 2. 9. A composition according to claim 1,wherein component (a) is a packaging material.
 10. A compositionaccording to claim 1, wherein component (a) is selected from the groupconsisting of an oil, a grease, a wax, a gel, an emulsion, afilm-forming binder, an inorganic solid, a paper, a fabric and anatural, semi-synthetic or synthetic polymer.
 11. A compositionaccording to claim 1, wherein component (a) is a synthetic polymer. 12.A composition according to claim 1, wherein component (a) is apolyolefin.
 13. A composition according to claim 1, wherein component(a) is polyethylene, polypropylene or polybutylene or a copolymerthereof with a monoolefin or diolefin.
 14. A composition according toclaim 1, wherein component (b) is present in an amount of 0.02 to 5%,based on the weight of component (a).
 15. A composition according toclaim 1, comprising in addition to components (a) and (b), furtheradditives.
 16. A composition according to claim 15, wherein the furtheradditives are phenolic antioxidants, light-stabilizers or processingstabilizers.
 17. A compound of the formula I

wherein R₁ is C₁-C₂₅alkyl, C₂-C₂₅alkenyl, C₂-C₂₅alkynyl, unsubstitutedor C₁-C₄alkyl-substituted phenyl; C₇-C₉phenylalkyl, unsubstituted orC₁-C₄alkyl-substituted C₅-C₈cycloalkyl; R₂, R₃ and R₄ are eachindependently of the others

R₅ is C₁-C₁₈alkylene, C₂-C₁₈alkylene which is interrupted by oxygen;C₂-C₁₈alkenylene, C₂-C₂₀alkylidene, C₇-C₂₀phenylalkylidene,C₅-C₈cycloalkylene, unsubstituted or C₁-C₄alkyl-substituted phenylene,R₆ and R₇ are each independently of one another hydrogen or C₁-C₈alkyl,R₈ is unsubstituted or C₁-C₄alkyl-substituted C₂-C₁₂alkylene; R₉ isC₁-C₂₅alkyl, C₂-C₂₅alkyl interrupted by oxygen; C₇-C₉phenylalkyl,unsubstituted or C₁-C₄alkyl-substituted C₅-C₈cycloalkyl; unsubstitutedor C₁-C₄alkyl-substituted phenyl; and n is
 1. 18. A compound accordingto claim 17, wherein R₁ is C₁-C₂₅alkyl, C₂-C₂₅alkenyl, C₃-C₂₅alkynyl,unsubstituted or C₁-C₄alkyl-substituted phenyl; C₇-C₉phenylalkyl orunsubstituted or C₁-C₄alkyl-substituted C₅-C₈cycloalkyl.
 19. A compoundaccording to claim 17, wherein R₁ is C₁₀-C₁₂alkyl, R₂, R₃ and R₄ areeach independently of the others

R₅ is C₂-C₄alkylene, R₆ and R₇ are each independently of one anothermethyl or ethyl, and n is
 1. 20. A method of protecting a corrodiblemetal substrate, which comprises applying to this substrate acomposition according to claim
 1. 21. (canceled)